Analysis of Gasoline Blends-By GC-using ASTM D 6839, IsO 22854

APPLICATION NOTE
Analysis of Gasoline Blends and Finished Gasoline using

Reformulyzer M4 according to ASTM D6839 & EN ISO 22854
Fast Analysis in 39 minutes

In compliance with key methods EN
ISO 22854 and ASTM D6839
Keywords:
Reformulyzer, Group-Type Analysis,
Finished Gasoline, Gasoline Blends
INTRODUCTION
X
X
X
X
X
X
X
X
X
X
X
X
X
60
39
15
E85
X
X
FAST
GROUP
TYPE
GASOLINE
PIANO
This application note describes the quantitative

determination of hydrocarbon types and
oxygenates in Gasoline Blends and Finished
Gasoline using the AC Reformulyzer M4.
PIONA
PONA
PIPNA
Depending on the sample stream or product, a

range of analytical modes can be used, ensuring
shortest possible runtimes, and data as required
for that specific product. See Table 1.
OPIONA
Light Straight Run

Naphtha
Heavy Straight Run
Naphtha
Depentanized Bottom
Reformate
FCC Light/Med/Heavy
Visbreaker
Alkylate / Isomerate
Gasoline Blend
Gasoline with Oxygenates
E85, E20
Analysis Time
OPNA
Typical modes used:
PNA
With the introduction of the 4th generation AC

Analytical Controls (AC) Reformulyzer M4, group
type analysis of finished gasoline and its precursors
& blend streams has become easier and much
faster than before.
The Reformulyzer M4 benefits from the use of
capillary/Micropacked columns and traps, resulting
in unprecedented speed of analysis, the widest
analytical range and excellent precision. It complies
with key methods EN ISO 22854 and ASTM D6839
and derived methods.
X
X
X
X
25
30
30
30
55
40
X
39
Table 1: Reformulyzer M4 Analysis Modes vs Product Streams
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APPLICATION NOTE
INSTRUMENTAL
The determination of different hydrocarbon types
and oxygenates is achieved by separation and
elution on a series of designed traps and columns.
The flow diagram for Reformulyzer M4 is shown
below in Figure 1, and the analysis schedule used
for this specific method is in Table 2. The Polar
Column separates the Paraffins and Naphthenes
from the Aromatics while Heavy Aromatics and
Alcohols are retained on the Pre-Column. Ethers
pass unretained and are trapped on the
Ether/Alcohol-trap to be analyzed on the Boiling
Point column. Paraffins and Naphthenes pass the
Olefin trap where Olefinic components are trapped.
Further separation of Saturates is on the 13X
Column resulting in a carbon number distribution.
By using multiple valves and columns the
Aromatics, PolyNapthenes and Alcohols are
analyzed on a Boiling Point Column in two different
Aromatic fractions. Between two aromatic fractions
the Olefin trap is desorbed in backflush and Olefins
are separated on 13X column. The Micropacked
traps and columns are located in the left side and
have separate heater elements for individual
temperature programming. This allows heating
and/or cooling of traps simultaneous, resulting in
total analysis runtime of 39 minutes.
From
(min)
To
(min)
Components
Column route
12
C4 to C11
N+P
1st Polar column fraction on

13X Column
12
15
Ethers
Trapped Ethers via E/A-trap

to Boiling Point Column
15
16
Saturates
> 185C
Backflush Boiling Point

Column
16
26
C4 to C11
CO+O
Backflush desorption of
Olefin trap on 13X Column
26
28
C6 to C8 A
and pN
2nd Polar Column fraction via

E/A-trap to Boiling Point
Column
28
39
Saturates
> 185C

Column of 2nd Polar Column
fraction
29
37
Alcohols +
C8 to C10 A
3rd Polar Column fraction via

E/A-trap to Boiling Point
Column
38
39
Aromatics
> 185C

Column of 3rd Polar Column
fraction
Table 2: Reformulyzer M4 Gasoline method
Pt flow (PCM B-1) H2

S/SL
A-flow (S/SL) N2
Pt-column
Polar column
Olefin trap
Precolumn
6
5
4
V1A
5
4
V2
V1
5
4
V3A
V3
1
2
5
4
V4
13 X
1
2
BP-Column
B-flow (PCM B-2) N2
5A trap
A/E trap
V5
FID
Figure 1: Reformulyzer M4 Flow Diagram
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APPLICATION NOTE
Gravimetric Blends and a Gasoline N Certified
Reference Materials (CRM) were analyzed using
the Reformulyzer M4 in Gasoline mode.
Representative chromatograms are shown below
and typical report outputs from the analysis for the
CRM are in Tables 3 and 4.
Chromatograms show clear group separations for

Paraffins, Naphthenes, Aromatics, Olefins and
Oxygenates, and %Weight and %Volume by
carbon numbers are well within specifications for
this particular CRM. Reported are compositions
in Weight% and Volume%.
Aromatics
Aromatics
Saturates
Ethers
10
Olefins
15
20
Alcohols
25
30
Figure 2: Reference Sample Gravimetric Blend (50.16.512) in Gasoline mode
35
40
Aromatics
Aromatics
Saturates
ETBE
Olefins
EtOH
10
15
20
25
30
35
40
Figure 3: Gasoline N CRM (00.02.048) in Gasoline mode

Normalized weight percent results
Cnr Naph. Paraf. Arom. Cycl Ol.
1
2
3
4
1.03
5
0.29 10.49
0.14
6
2.14
9.13
1.03
0.50
7
1.44
6.66 10.24
0.46
8
1.12
8.28 14.78
0.17
9
0.38
0.97
8.21
0.03
10
0.22
0.98
0.09
11+
0.21
0.27
Poly
Total
5.38 36.99 35.51
1.39
Normalized volume percent results

Olef.
0.55
3.52
2.77
1.79
0.94
0.27
9.84
Table 3: Reporting Gasoline N Weight%
Oxyg. Total
0.90
0.08
0.09
0.90
0.08
1.67
14.44
9.83 25.40
20.59
25.29
9.86
1.29
0.48
0.01
10.90
100
Cnr Naph. Paraf. Arom. Cycl Ol.

1
2
3
4
1.33
5
0.29 12.48
0.14
6
2.10 10.29
0.87
0.47
7
1.41
7.22
8.76
0.44
8
1.07
8.72 12.65
0.15
9
0.35
1.00
6.98
0.03
10
0.22
0.82
0.08
11+
0.21 0.237
Poly
Total
5.23 41.47 30.31
1.31
Olef.
0.67
4.00
3.01
1.90
0.98
0.27
10.83
Oxyg. Total
0.85
0.07
0.08
0.84
0.07
2.08
16.91
9.84 26.58
19.73
23.57
8.63
1.12
0.44
0.01
10.83 100.00
Table 4: Reporting Gasoline N Volume%
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APPLICATION NOTE
CONCLUSION
The Reformulyzer M4 provides reports group type
data in full accordance with key methods EN ISO
22854 and ASTM D6839.
Weight% and Volume% profile reports are
generated grouping Naphthenes, Paraffins, Olefins,
Aromatics and Oxygenates by carbon number as
well as the totals of the different groups and the
totals by carbon number.
Through the use of Capillary and Micropacked

columns and Traps The Reformulyzer M4 takes
only 39 minutes to produce reliable results in
Gasoline mode.
Specifications
Scope /
Separation Range
Finished gasoline
Reformer feed
Reformate
Straight naphtha
FCC naphtha/Olefins
Isomerates
Alkylate
E20+/E85
Paraffins C4-C11
Isoparaffins C4-C11
Olefins C4-C11
Naphthenes C5-C11
Aromatics C6-C11
Oxygenates C1-C6 (includes Methanol,
Ethanol, n-Propanol, i-Propanol, t-Butanol,
i-Butanol, 2-Butanol, tert-amylalcohol,
MTBE, ETBE, DIPE, TAME)
Method Compliance
According Methods
ASTM D6839, EN-ISO22854, ASTM D5443, IP566, SH/T 0741, GB/T 28768-2012
Ordering Information
CCG3500A
Reformulyzer M4 120V
CCG3500B
CCG3500C
Table 5: Reformulyzer M4 Specifications & Ordering Information
AC Analytical Controls has been the recognized leader in chromatography analyzers for gas, naphtha and gasoline streams in crude
oil refining since 1981. AC also provides technology for residuals analysis for the hydrocarbon processing industry. Applications cover
the entire spectrum of petroleum, petrochemical and refinery, gas and natural gas analysis; ACs Turn-Key Application solutions
include the AC Reformulyzer , SimDis, Hi-Speed RGA and Customized instruments.
00.00.239 2013/1 - Copyright 2013 PAC L.P. All rights reserved
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APPLICATION NOTE

Analysis of Gasoline Blends and Finished Gasoline using

Fast Analysis in 39 minutes

This application note describes the quantitative

Depending on the sample stream or product, a

Light Straight Run

Typical modes used:

With the introduction of the 4th generation AC

Table 1: Reformulyzer M4 Analysis Modes vs Product Streams

1st Polar column fraction on

Trapped Ethers via E/A-trap

Backflush Boiling Point

2nd Polar Column fraction via

Backflush Boiling Point

3rd Polar Column fraction via

Backflush Boiling Point

Table 2: Reformulyzer M4 Gasoline method

Pt flow (PCM B-1) H2

B-flow (PCM B-2) N2

Figure 1: Reformulyzer M4 Flow Diagram

Chromatograms show clear group separations for

Figure 2: Reference Sample Gravimetric Blend (50.16.512) in Gasoline mode

Figure 3: Gasoline N CRM (00.02.048) in Gasoline mode

Normalized volume percent results

Table 3: Reporting Gasoline N Weight%

Cnr Naph. Paraf. Arom. Cycl Ol.

Table 4: Reporting Gasoline N Volume%

Through the use of Capillary and Micropacked

Table 5: Reformulyzer M4 Specifications & Ordering Information

00.00.239 2013/1 - Copyright 2013 PAC L.P. All rights reserved

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